JPH0578562A - Thermoplastic resin composition - Google Patents

Abstract

PURPOSE:To obtain a thermoplastic resin composition improved in the compatibility between the constituent resins and having good heat resistance, mechanical properties, moldability and chemical resistance by adding zinc oxide to a composition comprising a polyarylene resin and a polyamide resin. CONSTITUTION:The objective composition is prepared by adding 0.01-5 pts.wt. zinc oxide or catalyst (A) prepared by homogeneously dispersing zinc oxide in silica and/or alumina and having a ratio of the number of moles of the Zn atoms to the total of the number of moles of the Si atoms and the number of moles of the Al atoms of 1:1 to 1:0.1 to 100 pts.wt. total of 95-5 pts.wt. polyarylate resins and 5-95 pts.wt. polyamide resin. This composition is markedly improved in the compatibility between the two resin by adding a suitable amount of component A and excels in heat resistance, chemical resistance, mechanical properties and moldability.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a thermoplastic resin composition containing a polyarylate resin and a polyamide resin as main components and having good heat resistance, mechanical properties, moldability and chemical resistance.

[0002]

2. Description of the Related Art Polyarylate resins have excellent heat resistance,
Since it has flame retardancy, mechanical properties, transparency, and dimensional stability, it is used in various applications such as electrical and electronic parts, precision machinery, and automobiles. However, since the polyarylate resin has insufficient solvent resistance, and has a defect that the melt viscosity is relatively high and the moldability is poor, the range applicable to the aromatic polycarbonate resin alone is limited. is the current situation.

Generally, it is difficult to obtain a resin composition having good properties such as heat resistance, mechanical properties, moldability and chemical resistance from a single resin. In the case of a crystalline resin, a polymer alloy with a crystalline resin is used to compensate for the drawback. Polyamide resin is a resin with excellent chemical resistance and fluidity, so by combining it with a polyarylate resin and polymerizing it into a polymer alloy, the advantages of both resins are combined to achieve good heat resistance, mechanical properties, moldability, and chemical resistance. It is expected that a thermoplastic resin composition will be obtained, but in reality, the polyarylate resin and the polyamide resin have poor compatibility, and the incompatible microphase-separated type resin cannot be obtained by simply mixing the two resins. Since the sea-island structure cannot be formed, it is difficult to obtain a thermoplastic resin composition having the advantages of the two resins.

[0004]

The object of the present invention is to improve the compatibility between the polyarylate resin and the polyamide resin so that the heat resistance, the mechanical properties, the moldability and the resistance to both of them have both advantages. It is to provide a thermoplastic resin composition having good chemical properties.

[0005]

Means for Solving the Problems As a result of various studies to improve the compatibility of the polyarylate resin and the polyamide resin, the present inventors have found that a composition of the polyarylate resin and the polyamide resin contains zinc oxide or silica and / or Or, by adding an appropriate amount of a catalyst in which zinc oxide is uniformly dispersed in alumina, and further kneading them, the compatibility between the polyarylate resin and the polyamide resin is significantly improved, and the heat resistance, mechanical properties, moldability, It was found that a composition having excellent chemical resistance was obtained, and the present invention was completed.

That is, the present invention relates to (a) 95 to 5 parts by weight of polyarylate resin, (b) 5 to 95 parts by weight of polyamide resin, and (c) 100 parts by weight of the total of the polyarylate resin and the polyamide resin. 0.01% zinc oxide
To 5 parts by weight, and (a) 95 to 5 parts by weight of polyarylate resin, (b) 5 to 95 parts by weight of polyamide resin, and (c) the polyarylate resin. And a total of 10 of the above polyamide resins
Zinc oxide is uniformly dispersed in silica and / or alumina with respect to 0 part by weight, and the number of moles of Zn atom: (the number of moles of Si atom + the number of moles of AL atom = 1: 1) to 1: 0.1.
The present invention relates to a thermoplastic resin composition, wherein 0.01 to 5 parts by weight of the catalyst is added.

The polyarylate resin used in the present invention is not particularly limited and is commercially available.
Polymerization method of reacting high-valent phenols with aromatic dicarboxylic acid in a high temperature solution state, in the presence of amine as a deoxidizing agent,
Solution polymerization method in which divalent phenols and aromatic dicarboxylic acid dichloride are reacted in an organic solvent, and divalent phenols and aromatic dicarboxylic acid dichloride are dissolved in two types of solvents that are incompatible with each other, and then an alkali is present. 2 below
It can be produced by an interfacial polymerization method in which the liquid is mixed and stirred and a polycondensation reaction is carried out at the interface.

Suitable dihydric phenols which can be used for the production of these polyarylate resins include 2,2-bis (4-hydroxyphenyl) propane (bisphenol A), resorcinol, hydroquinone and 2,2'-dihydroxy. There are diphenyl, 2,6-dihydroxynaphthalene, bis (4-hydroxyphenyl) sulfone, bis (4-hydroxyphenyl) sulfoxide, bis (4-hydroxyphenyl) ketone, bis (4-hydroxyphenyl) ether.

In producing the polyarylate resin, two or more dihydric phenols may be used, a homopolymer of dihydric phenols, a copolymer using two or more dihydric phenols, or a mixture thereof. Suitable aromatic dicarboxylic acids that can be used in the production of these polyarylate resins include, for example, terephthalic acid, isophthalic acid, naphthalenedicarboxylic acid and mixtures thereof, and alkyl-substituted homologs of these aromatic dicarboxylic acids. There are halides and the like.

The polyamide resin used in the present invention is not particularly limited and is commercially available. Hexamethylenediamine, decamethylenediamine, dodecamethylenediamine, 1,3- or 1,4-bis (amino). Methyl) cyclohexane, diamines such as aliphatic, alicyclic and aromatic such as m- or p-xylylenediamine, and aliphatic and fats such as adipic acid, sebacic acid, cyclohexanedicarboxylic acid, terephthalic acid and isophthalic acid Polyamide resins produced from dicarboxylic acids such as aromatics and aromatics, polyamide resins produced from lactams such as ε-caprolactam and ω-dodecalactam, and mixtures or copolymerized polyamide resins containing these components. Is exemplified.

Specific examples include polycaproamide (nylon 6) and polyhexamethylene adipamide (nylon 6).
6), polyhexamethylene sebacamide (nylon 6,1
0), polyhexamethylene dodecamide (nylon 6,1
2), polyundecane amide (nylon 11), polydodecane amide (nylon 12), polyxylylene adipamide, polyhexamethylene terephthalamide, polyphenylene phthalamide and the like. The degree of polymerization of the polyamide resin used here is not particularly limited, and one having a relative viscosity of 2.0 to 5.0 is usually preferable.

In the present invention, the polyarylate resin (a) and the polyamide resin (b) are (a) :( b) = 9.
5: 5 to 5:95 parts by weight, preferably 70:30 to 3
0:70 parts by weight, more preferably (a) :( b) = 6
It is mixed in the range of 0:40 to 40:60 parts by weight. When the compounding amount of the polyarylate resin is less than 5 parts by weight, heat resistance and mechanical properties are deteriorated, and when the compounding amount of the polyamide resin is less than 5 parts by weight, moldability and chemical resistance are deteriorated.

The catalyst used in the present invention, in which zinc oxide is uniformly dispersed in zinc oxide and silica and / or alumina, is an important component which functions as a reaction catalyst between the polyarylate resin and the polyamide resin. The zinc oxide used in the present invention is not limited in its production method. For example, a method of burning metallic zinc in air, a method of thermally decomposing zinc carbonate, or a method of oxidizing zinc nitrate and ammonia water or ammonia gas is used. It can be obtained by a method of obtaining zinc and drying it at a low temperature. Among the above-mentioned production methods, the method of obtaining zinc hydroxide from zinc nitrate and ammonia water or ammonia gas and drying it at a low temperature is preferable because the activity of zinc oxide is higher than that of other methods of treating at a high temperature. The characteristic value of the zinc oxide used in the present invention is not particularly limited, but preferably the average particle size is 0.01 to 20 μm, the specific surface area is 5 to 100 m ² / g, and more preferably the average particle size is Those having a surface area of 0.01 to ² μm and a specific surface area of 10 to 100 m ² / g are preferably used.

The catalyst used in the present invention in which zinc oxide is uniformly dispersed in silica and / or alumina is added to an aqueous solution of zinc inorganic salts by adding an aqueous solution of tetraethoxysilane and / or aluminum inorganic salts, and further by adding aqueous ammonia. By adding or blowing ammonia gas, a catalyst in which zinc hydroxide is uniformly dispersed at a very micro level in a hydrogel lattice is prepared.
It can be obtained by drying at 0 ° C and baking at 300 to 500 ° C.

As the inorganic salts, zinc nitrate is preferable since the activity of the catalyst is large. The compounding ratio of zinc inorganic salt, tetraethoxysilane, and aluminum inorganic salt is as follows: mol number of Zn atom: (mol number of Si atom + A
The number of moles of 1 atom) must be in the range of 1: 1 to 1: 0.1. When (the number of moles of Si atom + the number of moles of Al atom) exceeds 1, the catalytic activity decreases because the content of zinc oxide in the catalyst decreases, and when it is less than 0.1, the dispersion of zinc oxide in the catalyst is reduced. Results in poor catalyst activity.

With respect to 100 parts by weight of a resin composition in which a polyarylate resin and a polyamide resin are mixed in a predetermined ratio,
Compatibility is achieved by mixing 0.01 to 5 parts by weight, preferably 0.1 to 1.5 parts by weight, of a catalyst in which zinc oxide is uniformly dispersed in zinc oxide or silica and / or alumina. It is possible to greatly improve the compatibility between the polyarylate resin, which has almost no occurrence of the above, and the polyamide resin. If the added amount of the catalyst in which zinc oxide is dispersed in zinc oxide or silica and / or alumina is less than 0.01 parts by weight, the reaction between the polyarylate resin and the polyamide resin becomes insufficient and the compatibility improving effect is insufficient. Therefore, properties such as heat resistance, mechanical properties, moldability, and chemical resistance deteriorate. If the addition amount of the catalyst in which zinc oxide is uniformly dispersed in zinc oxide or silica and / or alumina exceeds 5 parts by weight, the compatibility between the polyarylate resin and the polyamide resin becomes too good and the incompatible micro phase separation occurs. Since the mold-island structure cannot be obtained, heat resistance, mechanical properties, moldability, chemical resistance, and other properties deteriorate.

To the composition of polyarylate resin and polyamide resin, a proper amount of a catalyst in which zinc oxide or zinc oxide is uniformly dispersed in silica and / or alumina is added, and the mixture is kneaded to obtain heat resistance and mechanical properties. A composition having excellent moldability and chemical resistance can be obtained. The reason is that a catalyst in which zinc oxide is uniformly dispersed in zinc oxide or silica and / or alumina acts as a reaction catalyst to cause a reaction between the polyarylate resin and the polyamide resin,
A reaction product containing a polyarylate component and a polyamide component in the same molecule acts as a surfactant to improve the compatibility between the polyarylate resin and the polyamide resin, and to form an incompatible microphase-separated sea-island structure. It is thought that it is possible to take.

The composition of the present invention may further contain other compounding agents, for example, inorganic fillers such as talc, mica, calcium carbonate and wollastonite, or reinforcing agents such as glass fiber and carbon fiber, depending on the use or purpose. A flame retardant, a flame retardant auxiliary, an antistatic agent, a stabilizer against heat, oxidation and light, a pigment, a release agent, etc. can be added.

As a method for producing the thermoplastic resin composition of the present invention, a conventionally known method can be applied, and the raw material of the thermoplastic resin composition of the present invention is batched or divided into a Henschel mixer. It can be obtained by sufficiently mixing and further kneading with a biaxial kneader at a resin temperature in the range of 240 ° C to 270 ° C. When the resin temperature is lower than 240 ° C., the polyarylate resin tends not to melt and becomes poorly dispersed, and when the resin temperature exceeds 270 ° C., the composition tends to foam due to thermal decomposition, so that kneading is performed within the above temperature range. Preferably.

[0020]

【Example】

Example 1 An aqueous zinc nitrate solution (0.1 mol / l) and aqueous ammonia (0.2 mol / l) were mixed in equal amounts at room temperature, and the obtained zinc hydroxide precipitate was washed with water and then spray dried. It was dried to obtain zinc oxide A. As a result of measurement using a centrifugal sedimentation method, the average particle diameter was 0.4 μm.
In addition, as a result of measurement using the nitrogen adsorption method, the specific surface area is 7 m ^2.
/ G.

Polyarylate resin (U polymer R U-1
060, Unitika Ltd. 92 parts by weight, polyamide resin (UBE Nylon 1013FB, Ube Industries Ltd.)
Add 8 parts by weight and 4 parts by weight of homemade zinc oxide to a Henschel mixer and mix at 800-1200 rpm for several minutes.
This was melt-kneaded with a twin-screw kneader under conditions such that the resin temperature was 250 to 270 ° C. to prepare pellets, and then injection molding was performed. The bending strength, tensile strength and chemical resistance were evaluated. The evaluation results are shown in Table 1.

Example 2 Aqueous zinc nitrate solution (0.1 mo
1 / l) and tetraethoxysilane (0.1 mol / l)
And an aqueous ammonia solution (0.6 mol / l) are mixed in equal amounts at room temperature, and the resulting precipitate is washed with water and then spray dried.
Zinc oxide B was obtained by drying in a machine and then at 350 ° C. for 8 hours.

Polyarylate resin (U polymer R U-1
060, manufactured by Unitika Ltd., 8 parts by weight, polyamide resin (UBE nylon 1013FB, produced by Ube Industries, Ltd.) 9
2 parts by weight and 0.3 part by weight of home-made zinc oxide B are put into a Henschel mixer and mixed for several minutes at 800 to 1200 rpm, and the resin temperature is 250 to 270 with a twin-screw kneader.
Melt kneading to make pellets under the condition of ℃, injection molding was performed, and the heat distortion temperature, bending strength, tensile strength and chemical resistance of the obtained test pieces were evaluated together with the evaluation of the moldability. .. The evaluation results are shown in Table 1.

<< Examples 3 to 5 >> The mixture preblended with the composition shown in Table 1 was melt-kneaded in the same manner as in Example 1,
After molding, its characteristics were evaluated. The evaluation results are also shown in Table 1.

<< Comparative Examples 1 to 4 >> The mixture preblended with the composition shown in Table 2 was melt-kneaded in the same manner as in Example 1,
After molding, its characteristics were evaluated. Evaluation results are also shown in Table 2
Shown in.

[0026]

[Table 1]

[0027]

[Table 2]

* 1 Heat distortion temperature: Constant speed (2 ° C /
When the temperature was raised by 1 minute, the test piece was constantly loaded (18.6 Kg
/ Cm ² ), the temperature at the time of bending by a predetermined amount (0.25 mm) is measured according to ASTM D486. * 2 Bending strength: Measured according to ASTM D-790. * 3 Tensile strength: Measured according to ASTM D-638. * 4 Chemical resistance: The bending test piece was immersed in methyl ethyl ketone at 25 ° C. for a whole day and night, and the minimum stress value (critical stress value) at which solvent cracking occurred was measured. In the table, ◯ indicates a critical stress value of 140 Kgf / cm ² or more, Δ indicates 100 to less than 140 Kgf / cm ² , and X indicates less than 100 Kgf / cm ² . * 5 Moldability: Toshiba Machine Co., Ltd. injection molding machine IS8
With 0 EPN (maximum injection amount 3 oz), heating cylinder temperature 2
A relay box was molded at 80 ° C to 330 ° C. The table shows the molding cycle and mold temperature at that time.

[0029]

As is apparent from Tables 1 and 2, the thermoplastic resin composition of the present invention obtained by the melt reaction has good heat resistance which is a characteristic of polyarylate resin, and polyamide resin. It is a new and well-balanced material with good chemical resistance and moldability, which are the characteristics of.

─────────────────────────────────────────────────── ───

[Procedure amendment]

[Submission date] August 28, 1992

[Procedure Amendment 1]

[Document name to be amended] Statement

[Correction target item name] 0021

[Correction method] Change

[Correction content]

Polyarylate resin (U polymer R U
100 , manufactured by Unitika Ltd., 92 parts by weight, polyamide resin (UBE nylon 1013FB, produced by Ube Industries, Ltd.)
Add 8 parts by weight and 4 parts by weight of homemade zinc oxide to a Henschel mixer and mix at 800-1200 rpm for several minutes.
This was melt-kneaded with a twin-screw kneader under conditions such that the resin temperature was 250 to 270 ° C. to prepare pellets, and then injection molding was performed. The bending strength, tensile strength and chemical resistance were evaluated. The evaluation results are shown in Table 1.

[Procedure Amendment 2]

[Document name to be amended] Statement

[Name of item to be corrected] 0023

[Correction method] Change

[Correction content]

Polyarylate resin (U polymer R U
100 , Unitika Co., Ltd. 8 parts by weight, polyamide resin (UBE Nylon 1013FB, Ube Industries Ltd.) 9
2 parts by weight and 0.3 part by weight of home-made zinc oxide B are put into a Henschel mixer and mixed for several minutes at 800 to 1200 rpm, and the resin temperature is 250 to 270 with a twin-screw kneader.
Melt kneading to make pellets under the condition of ℃, injection molding was performed, and the heat distortion temperature, bending strength, tensile strength and chemical resistance of the obtained test pieces were evaluated together with the evaluation of the moldability. .. The evaluation results are shown in Table 1.

Claims (2)

[Claims] 1. A total of 10 parts of (a) 95 to 5 parts by weight of polyarylate resin, (b) 5 to 95 parts by weight of polyamide resin, and (c) the polyarylate resin and the polyamide resin.
A thermoplastic resin composition, characterized in that 0.01 to 5 parts by weight of zinc oxide is added to 0 parts by weight. 2. A total of 10 parts of (a) 95 to 5 parts by weight of polyarylate resin, (b) 5 to 95 parts by weight of polyamide resin, and (c) the polyarylate resin and the polyamide resin.
Zinc oxide is uniformly dispersed in silica and / or alumina with respect to 0 part by weight, and the number of moles of Zn atom: (the number of moles of Si atom + the number of moles of Al atom) = 1: 1 to 1: 0.1
0.01 to 5 parts by weight of the catalyst is added to the thermoplastic resin composition.